New anthraquinone vat dyestuffs



2,778,837 Patented Jan. 22, 1957 United States Patent ce 1-nitroanthraquinone-2-carboxylic acid, and 2,778,837 1-chloranthraqu1none-2-carboxyllc acid.

NEW AN THRAQUINONE VAT DYESTUFFS Theodor Holbro, Basel, Switzerland, assignor to Ciba Limited, Basel, Switzerland, a firm of Switzerland No Drawing. Application July 6, 1954, Serial No. 441,635

Claims priority, application Switzerland July 29, 1953 5 Claims. (Cl. 260--316) The reaction of the 5:5'-diamino-1:1'-dianthrimide is 5 advantageously carried out in a solvent or diluent, preferably one of high boiling point such as monochlorobenzene, dior tri-chlorobenzenes, nitrobenzene or naphthalene, at a raised temperature, for example, between about 100 C. and the boiling point of the solvent or diluent used.

When it is necessary to convert in the resulting products into amino groups substituents present in the l-position of the radical R2, this conversion may be carried out by methods in themselves known. For example, nitro This invention provides valuable new anthraquinone groups are advantageously converted into amino groups vat dyestuffs which, like, for example, the dyestufi of by vatting the dyestuti in an aqueous alkaline medium the constitution with a quantity of sodium hydrosulfite suificient also to (1) NH: HRN

reduce the nitro groups, and isolating the product in the usual manner, for example, by introducing air to precipitate the product from the vat, or by treating the dyestutf RZ OO HN R NH O with ammonia or an agent yielding ammonia, for ex- 111 p the radical of a ample, in nitrobenzene at a raised temperature. 5=5'-d1am1110-1:ljdlanthnrplde-carbazole, and 2 p If desired, the dyestuffs so obtained may be subjected ent$ an aflthraqulhohh fadlcal to which the group to further reactions. Thus, for example, they may be 15 hh 111 the l-posltloll and the p in the treated with halogenating agents or, When they contain -P P' D reactive substituents, further reactions may be carried The lllventloh also Pf a Process for making the out with these substituents. For example, nitro groups ab0ve y l Whefeln a 5i5'-diamino'lil'-dianthrim' in the 4-position of the radical R2 may be reduced and lde-carbazole is reacted with an anthraquinone 2-carboxh resulting amino rou which are considerably more yllcacld or a functional derivative thereof which contains 40 reactive h th i th 1- itimay b lated, in the l-po-sition an amino group or a substituent 0011- for example, .benzoylated. Verhhle an amino gfQuP, when necessary, the The new vat dyestuffs corresponding to the Formula 2 latter sub$t1tu111t 1S cohverthd into an amino pabove, if desired, after further treatment in the manner AS Starting material, which Provides the radical described above, can be used in known manner as such f there 18 advflntagfiously used 5 or in the form of their leuco ester salts obtainable by .dl3imlIlO'1.: l' dianthrilmide-carb azole AS a startknown methods for tor printing a very wide a -img material introducing the acyl radical of the constituety f fib rs, li l fib d especially U011 there is advantagwusly used a vegetable fibers, and therefore for dyeing or printing active functional derivative of a l-arninoanthraquinone- 1 or ilk, d dvantageously cotton, linen, artificial z'carboxyhc acid Of all amhmquinonea'cal'bflxylic silk or staple fibers 0f regenerated cellulose and also polyacid which contains in the 1-position a substituent conamide fib The dygings and prints produced on vel'fible into an amino group, for l halogen ous fibers are of very similar to identical tints and are disatom or a nitro group. If desired, these compounds may a i h d by very good properties of fastness. contain further Substituents, fflrlexample, additional nitro The following examples illustrate the invention, the groups OI halogen aloms, nitll'le p alkOXY groups parts and percentages being by weight unless otherwise acylamhlo p Among the leactivh functional stated and the relationship of parts by weight to parts by derivatives of such carboxylic acids the acid halides, and volume b i h same as h t f th kilogram t the above all the acid chlorides, yield especially good results. i As examples there may be mentioned the halides of the following acids: 7

correspond to the general formula (2) NH: HzN

Example 1 45.7 parts of 5:5'-diamino-l:1'-dianthrimide-carbazole and parts of 1-nitroanthraquinone-2-carboxylic acid chloride are stirred in 1080 parts of dry nitrobenzene for 2 hours at -150 C. and then for 3 hours at C. The mixture is then cooled, and the reaction 1-aminoanthraquinone-2-carboxylicacid,

1amino-4-chloranthraquinone-2-carboxylic acid, 1-amino-4-nitroanthraquinone-2-carboxylic acid, 1amino-4-cyanoanthraquinone-2-carhoxylic acid,

3 product is filtered oil with suction, washed with nitrobenzene and freed from adherent solvent by steam distillation. After being filtered and dried, the reaction product is obtained in excellent yield in the form of an orange brown powder.

101.5 parts of the dinitro-compound so obtained, after being pasted with 162 parts of ethanol, are stirred with 7000 parts of water at 50 C. and, after the addition of 1350 parts 'of sodium hydroxide solution of 30 percent strength and 508 parts of sodium hydrosulfite, the product is vatted for one hour at 50-55 C. After this reduction air is introduced and the precipitated dyestuff is filtered 01f, washed and dried. There is obtained in quantitative yield a dark powder which dissolves in sulfuric acid with a violet coloration and dyes cotton from a red-brown vat very fast red tints.

Example 2 45.7 parts of :5-diamino-l:1-dianthrimide-carbazole and 62 parts of l-amino-anthraquinone-Z-carboxylie acid worked up as described in the first paragraph of Example 1. There is obtained in this manner in excellent yield a product corresponding to the dyestuif described in the second paragraph of Example 1.

By using instead of l-axninoanthraquinon'e-2-carboxylic acid chloride, l-arnino-4-cyanoanthraquinone-2-carboxylic acid chloride, there is obtained a product which dyes cotton from a red-brown vat pure orange-red tints.

By using 1-amino-4-bromanthraquinone-2-carboxylic acid a dyestuff is obtained which dyes cotton from. an orange-brown vat somewhat more brownish red tints than those of the dyestuif described in the first paragraph.

By reacting 5 :5 '-diaminol l. -dianthrimidecarbazole with 1-amino-4-nitroanthraquinonc-Z-carboxylic acid chloride in the manner described above, reducing the resulting product by vetting and reprecipitating it, and acylating the product with 2 mols of benzoyl chloride, there is obtained a dyestufi which dyes cotton from a violet-brown vat brown tints.

Example 3 45.7 parts of 5:5-diamino1:1-dianthrin1ide-carbazole and 67 parts of 1-chloranthraquinone-Z-carboxylic acid chloride are stirred in 1800 parts of dry nitrobenzene for 4 hours at 150-160" C. The reaction product is filtered oif with suction at 100 C., washed with nitrobenzene, and freed from adherent solvent by steam distillation. After filtering and drying the reaction product, it is obtained in very good yield in the form of a brownish orange powder which dissolves in concentrated sulfuric acid with an olive coloration and dyes cotton from an orangebrown vat yellow tints.

100' parts of the product so obtained are introduced into a mixture, which has previously been stirred for /2 hour at 170 C., of 72 parts of para-toluene sulfonamide and 41 parts of potassium carbonate in 1000 parts of nitrobenzen-e, and, after the addition of 2 parts of cuprous chloride, the whole is stirred for hours at 180-185 C. The mixture is then cooled, diluted at 70 C. with ethanol, the reaction product is filtered ofi with suction, washed with ethanol to remove the solvent, and freed from cuprous chloride by boiling it with dilute O NH:

4 hydrochloride acid. After being filtered off, washed and dried, the reaction product is obtained in very good yield in the form of an ochre-colored powder which dissolves in concentrated sulfuric acid with a violet coloration.

parts of the resulting product are introduced at 20 C. into 450 parts of sulfuric acid of 92.5 percent strength, and the whole is stirred for 40 minutes at C. The mixture is then poured on to 5000 parts of ice water, and the precipitated dyestuil is filtered off with suction, washed neutral with water and dried. The dyestufi is obtained in excellent yield and corresponds in its properties to the dyestuif described in the second paragraph of Example 1.

Example 4 1 part of the dy-estuff of Example 1 is well pasted with 8 parts by volume of sodium hydroxide solution of 30 percent strength and 200 parts of water at 25-30 C., 2 parts of sodium hydrosulfite are then added, and vatting is carried on for /2 hour at C. The solution is poured into a solution of 2 parts by volume of sodium hydroxide solution of 30 percent strength and 1 part of sodium hydrosulfite in 1800 parts of water. 100 parts of cotton are dyed in the resulting bath for one hour at 40-50 C. After hour, dyeing is carried out by the addition of 20 parts of sodium chloride or anhydrous sodium sulfate. The material is then squeezed, oxidized in the air, rinsed, and developed at the boil for /2 hour in a solution which contains in 1000 parts by volume of water 5 parts of soap and 2 parts of anhydrous sodium carbonate. The cotton is dyed a fast red tint.

Example 5 30 parts of the dyestuif described in Example 1, 140 parts of water, 600 parts of potassium carbonate thickening, 30 parts of sodium hydroxide solution of 30 percent strength and 20 parts of sodium formaldehyde sulfoxylate are mixed together, heated to 5 0 C. and then ground. By the addition of a further parts of sodium formaldehyde sulfoxylate and parts of urea, there is obtained a paste ready for printing. Cotton or other vegetable fibers can be printed in the normal manner with this paste. After being printed the material is dried, steamed for 8 minutes, rinsed with a solution containing per liter of water 3 grams of sodium perbora e and 2 grams of acetic acid of 40 percent strength, oxidized for 5 minutes, rinsed, soaped at the boil, again rinsed, and dried. In this manner a very fast brick red print is produced.

What is claimed is:

1. An anthraquinone vat dyestuif of the formula HrN 0 2,778,837 5 3. The anthraquinone vat dyestufi 0f the formula 0 N O: HIN O OO-EN- NHOC I 9) ON NH NO 0 4. The anthraquinone vat dyestuff of the formula NH: H|N

C0-HN NEE-00 ooo- =0 ll 11 0 B1 NE Br 0 J 5. The anthraquinone vat dyestuif of the fqmmla O NH:

O O-EN ll 0 H 1,819,014 Baumann Aug. 18, 1931 2,567,822 Moergeli Sept. 11, 1951 FOREIGN PATENTS 580,642 Great Britain Sept. 6, 1946 OTHER REFERENCES Das Anthrencen und die Anthrachinone, Houben, Georg Thieme. Pub. Leipzig (1929), pp. 497-501. 

1. AN ANTHRAQUINONE VAT DYESTUFF OF THE FORMULA 